Solvent-resistant polyphenylene ether resin composition

ABSTRACT

A polyphenylene ether resin composition having improved solvent resistance comprising (A) a modified polyphenylene ether obtained by modifying a polyphenylene ether with a modifier such as maleic anhydride and (B) a modified polyolefin obtained by modifying a polyolefin with both a modifier such as maleic anhydride and a vinyl or vinylidene compound such as styrene, and optionally (C) a binder such as phenylenediamine.

This application is a division of application Ser. No. 122,235, filedNov. 17, 1987, now U.S. Pat. No. 4,914,153.

This invention relates to a novel polyphenylene ether resin compositionhaving excellent solvent resistance in addition to excellent mechanicalstrength and moldability. More specifically, it relates to a novelpolyphenylene ether resin composition having improved solvent resistancecomprising a modified polyphenylene ether and a modified polyolefin andhaving excellent mechanical strength and moldability.

Polyphenylene ethers are polymeric materials having superior thermalresistance and being useful as engineering plastics. It is well knownhowever that polyphenylene ethers have inferior solvent resistance andpoor moldability.

As a technique of improving the moldability or flow characteristics, ofpolyphenylene ether, U.S. Pat. No. 3,383,435 discloses the blending of apolystyrene resin. Japanese Laid-Open Patent Publication No. 12894/1977discloses the blending of a rubber-reinforced copolymer of styrenecompound and an alpha,beta-unsaturated dicarboxylic acid anhydride.These techniques, however, have not resulted in improvement of thesolvent resistance of polyphenylene ethers.

U.S. Pat. No. 3,361,851 discloses a technique of improving the solventresistance of a polyphenylene ether by blending it with a polyolefin.Since the polyphenylene ether has poor compatibility with thepolyolefin, only up to 10 % by weight, based on the total weight of thetwo resins, of the polyolefin can be blended, and the solvent resistanceand moldability of the polyphenylene ether cannot be satisfactorilyimproved by this technique.

Various attempts have been made to improve the compatibility of thepolyolefin with the polyphenylene ether and the solvent resistance andmoldability of the polyphenylene either resin composition byincorporating a large amount of the polyolefin into polyphenylene ether.For example, Japanese Patent Publication No. 22344/1981 discloses atechnique of grafting a styrene compound to a polyolefin andincorporating the grafted polyolefin in a polyphenylene ether. JapaneseLaid-Open Publications Nos. 108153/1982 and 225150/1983 disclose atechnique of blending a polyolefin having glycidyl methacrylate or thelike copolymerized therewith with a polyphenylene ether. JapaneseLaid-Open Patent Publication No. 260649/1985 discloses a technique ofblending a modified copolymer obtained by polymerizing a copolymer ofglycidyl (meth)acrylate and an olefin with a styrene compound, with apolyphenylene ether. These prior techniques are directed to theimprovement of the compatibility of a polyolefin by incorporating astyrene structure and/or a glycidyl structure having excellentcompatibility with a polyphenylene ether. Certainly, they resulted in acertain degree of improvement in compatability, but the solventresistance and mechanical strength of polyphenylene ethers were notsufficiently improved. Hence, no practically satisfactory moldingmaterial of a blend of a polyphenylene ether with a modified polyolefincan be obtained by this technique. This is presumably because thesemodifying techniques rely only on the modification of the polyolefin andno modification is carried out on the polyphenylene ether, andconsequently, no positive chemical bond is formed between thepolyphenylene ether and the polyolefin.

It is an object of this invention to provide a novel resin compositionof a polyphenylene ether and a polyolefin having improved solventresistance with improved compatibility between the two. Specifically, byintroducing a chemical bond between the polyphenylene ether and thepolyolefin resin, the invention provides a polyphenylene ether resincomposition having good solvent resistance and mechanical strength aswell as good moldability.

According to this invention, there is provided a composition comprising

(A) a modified polyphenylene ether obtained by modifying a polyphenyleneether with a modifier selected from organic compounds having in themolecule (a) an ethylenic double bond and (b) a functional groupselected from the class consisting of a carboxyl group, an acidanhydride group and an epoxy group in the presence or absence of aradical initiator, and

(B) a modified polyolefin obtained by modifying a polyolefin with both amodifier selected from organic compounds having in the molecule (a) anethylenic double bond and (b) a functional group selected from the classconsisting of a carboxyl group, an acid anhydride group, an epoxy groupand an alcoholic hydroxyl group and a vinyl or vinylidene compound inthe presence or absence of a radical initiator.

This resin composition shows not only excellent solvent resistance butalso excellent moldability and mechanical properties as a result of amarked improvement in the compatibility of the polyphenylene ether withthe polyolefin.

In a preferred embodiment, a resin composition having a further improvedsolvent resistance and mechanical properties is provided by furtherincorporating (C) a binder selected from organic compounds having in themolecule at least two functional groups selected from the classconsisting of a carboxyl group, ester groups, an amide group, a hydroxylgroup, an amino group, a mercapto group and an epoxy group.

The modified polyphenylene ether and the modified polyolefin used in theresin composition of this invention denote a polyphenylene ether and apolyolefin modified by the methods to be described hereinafter.

The polyphenylene ether may be a homopolymer or a copolymer and isobtained by polycondensing at least one substituted monocyclic phenol ofgeneral formula (I). ##STR1## wherein R₁ represents an alkyl grouphaving 1 to 3 carbon atoms, and R₂ and R₃ each represent a hydrogen atomor an alkyl group having 1 to 3 carbon atoms.

Examples of the substituted monocyclic phenol of general formula (I)include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol,2-methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol,o-cresol, 2,3-dimethylphenol, 2,3-diethylphenol, 2,3-dipropylphenol,2-methyl-3-ethylphenol, 2-methyl-3-propylphenol, 2-ethyl-3-methylphenol,2-ethyl-2-propylphenol, 2-propyl-3-methylphenol, 2-propyl-3-ethylphenol,2,3,6-trimethylphenol, 2,3,6-triethylphenol, 2,3,6-tripropylphenol,2,6-dimethyl-3-ethylphenol and 2,6-dimethyl-3-propylphenol. Thus,illustrative of polyphenylene ethers obtained by polycondensing at leastone of these phenols are poly(2,6-dimethyl-1,4-phenylene)ether,poly(2,6-diethyl-1,4-phenylene)ether,poly(2,6-dipropyl-1,4-phenylene)ether,poly(2-methyl-6-ethyl-1,4-phenylene)ether,poly(2-methyl-6-propyl-1,4-phenylene)ether,poly(2-ethyl-6-propyl-1,4-phenylene)ether,2,6-dimethylphenol/2,3,6-trimethylphenol copolymer,2,6-dimethylphenol/2,3,6-triethylphenol copolymer,2,6-diethylphenol/2,3,6-trimethylphenol copolymer, and2,6-dipropylphenol/2,3,6-trimethylphenol copolymer.

Poly(2,6-dimethyl-1,4-phenylene)ether and2,6-dimethylphenol/2,3,6-trimethylphenol copolymer are especiallypreferred for use in this invention.

The polyolefin as used herein is a crystalline or amorphous olefinpolymer. Specific examples include homopolymers of olefins such aspolypropylene, low-density polyethylene, high density polyethylene,linear low-density polyethylene, propylene/ethylene copolymer, andpoly-4-methylpentene-1; and copolymers of a predominant proportion ofolefins with vinyl monomers copolymerizable therewith such as acrylicesters, methacrylic esters and glycidyl (meth)acrylate. Thesepolyolefins are used either singly or in combination. Of thesepolyolefins, polyethylene and polypropylene are preferred. Polypropyleneis especially preferred. These polyolefins may be produced by methodsknown to those skilled in the art, for example the methods described inENCYCLOPEDIA OF POLYMER SCIENCE AND TECHNOLOGY, volume 6, page 275(1967) and volume 11, page 597 (1969), published by John Wiley & Sons,Inc.

The "modifier" for the polyphenylene ether is an organic compound havingin the molecule (a) an ethylenic double bond and (b) functional groupselected from the class consisting of a carboxyl acid, an acid anhydridegroup and an epoxy group. Specific examples includealpha,beta-unsaturated dicarboxylic acids such as maleic acid,chloromaleic acid, citraconic acid and itaconic acid; unsaturatedmonocarboxylic acids such as acrylic acid, crotonic acid, vinylaceticacid, methacrylic acid, pentenoic acid and angelic acid; anhydrides ofthese alpha,beta-unsaturated dicarboxylic acids and unsaturatedmonocarboxylic acids; unsaturated epoxy compounds which are the reactionproducts between epichlorohydrin and the above alpha,beta-unsaturateddicarboxylic acids or unsaturated monocarboxylic acids, for exampleglycidyl maleate, glycidyl acrylate and glycidyl methacrylate. Maleicacid, acrylic acid, methacrylic acid, maleic anhydride, glycidylmethacrylate and glycidyl acrylate are preferred, and maleic anhydride,glycidyl methacrylate and glycidyl acrylate are especially preferred.

The modifier for the polyolefin used in this invention is selected fromthe aforesaid organic modifier compounds for the polyphenylene ether andin addition, organic compounds having (a) an ethylenic double bond and(b) an alcoholic hydroxyl group in the molecules (unsaturated alcoholcompounds). Specific examples of these compounds include hydroxyunsaturated monocarboxylic acid esters derived from the aforesaidunsaturated monocarboxylic acids and aliphatic diols such as ethyleneglycol, propylene glycol, trimethylene glycol, butane-1,4-diol,tetramethylene glycol or pentamethylene glycol or aliphatic polyols suchas glycerol, trimethylolpropane and pentaerythritol;polyhydroxy-alpha,beta-unsaturated dicarboxylic acid diesters derivedfrom the aforesaid alpha,beta-unsaturated dicarboxylic acids and theaforesaid aliphatic diols or polyols; hydroxy unsaturated monocarboxylicacid amides derived from the aforesaid unsaturated monocarboxylic acidsand aliphatic aminoalcohols; amides or imides ofhydroxy-alpha,beta-unsaturated dicarboxylic acids derived fromalpha,beta-unsaturated dicarboxylic acids and aliphatic aminoalcohols;and aliphatic unsaturated alcohols such as allyl alcohol, crotylalcohol, methyl vinyl carbinol, methyl allyl carbinol and methylpropenyl carbinol. Of these organic compounds, the hydroxy unsaturatedmonocarboxylic acid esters and polyhydroxy-alpha,beta-unsaturateddicarboxylic acid diesters are preferred. Specific examples of the theseorganic compounds are 2-hydroxyethyl acrylate, 2-hydroxyethylmethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,bis-2-hydroxyethyl maleate and bis-2-hydroxypropyl maleate.

The vinyl or vinylidene compound used in combination with the modifierfor the polyolefin denotes an alph,beta-unsaturated compound having apolymerizable vinyl or vinylidene group, which is not encompassed withinthe above modifiers. Examples of the vinyl or vinylidene compoundinclude aromatic vinyl or vinylidene compounds such as styrene,alpha-methylstyrene, methylstyrene, chlorostyrene, bromostyrene,divinylbenzene, hydroxystyrene and aminostyrene; alkyl (meth)acrylatessuch as methyl (meth)acrylate, ethyl (meth)acrylate, propyl(meth)acrylate and octyl (meth)acrylate; cyanovinyl compounds such asacrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate;and vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butylvinyl ether. Of these, the aromatic vinyl or vinylidene compounds andalkyl (meth)acrylates are preferred, and styrene is most preferred.

The modified polyphenylene ether and the modified polyolefin used inthis invention can be prepared, for example by the following methods.For example, the modified polyphenylene ether may be prepared bymelt-kneading and thus reacting the polyphenylene ether and the modifierat a temperature of 150° to 350° C. in a roll mill, a Banbury mixer, anextruder or the like; or by reacting the polyphenylene ether and themodifier under heat in a solvent such as benzene, toluene, xylene,decalin or tetralin. Likewise, the modified polyolefin can be preparedby melt-kneading and thus reacting the polyolefin, the modifier and thevinyl or vinylidene compound at a temperature of 150° to 300° C. in aroll mill, a Banbury mixer, an extruder or the like; or by reacting themunder heat in a solvent such as benzene, toluene, xylene, decalin ortetralin. The presence of a radical initiator, for example an organicperoxide such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxideor t-butyl peroxybenzoate, or an azo compound such asazobisisobutyronitrile or azobisisovaleronitrile in the reaction systemis effective for carrying out the modifying reaction easily. A morepractical modifying method is the melt-kneading in the presence of aradical initiator.

To improve the properties of the resin composition of this inventionincluding solvent resistance further, incorporation of a binder (C) iseffective. The binder (C) denotes an organic compound containing in themolecule at least two functional groups selected from a carboxyl group,an ester group, an amide group, a hydroxyl group, an amino group, amercapto group and an epoxy group. In this binder compound, two carboxylgroups may form an acid anhydride group. Specific examples of the binderinclude aromatic polycarboxylic acids such as terephthalic acid,isophthalic acid, phthalic acid, p-carboxyphenylacetic acid,p-phenyenediacetic acid, m-phenylenediglycollic acid,p-phenylenediglycollic acid, diphenyldiacetic acid,diphenyl-p,p'-dicarboxylic acid, diphenyl-m,m'-dicarboxylic acid,diphenyl-4,4'-diacetic acid, diphenylmethane-p,p'-dicarboxylic acid,diphenylethane-p,p'-dicarboxylic acid, stilbenedicarboxylic acid,benzophenone-4,4'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid,naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid,naphthalene-2,7-dicarboxylic acid, p-carboxyphenoxyacetic acid andtrimellitic acid; aliphatic polycarboxylic acids such as oxalic acid,succinic acid, adipic acid, cork acid, azelaic acid, sebacic acid,dodecanedicarboxylic acid and undecanecarboxylic acid; anhydrides ofthese aromatic or aliphatic polycarboxylic acids; aliphatic polyolcompounds such as ethylene glycol, propylene glycol, trimethyleneglycol, butane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,3-diol,cis-2-butene-1,4-diol, trans-2-butene-1,4-diol, tetramethylene glycol,pentamethylene glycol, hexamethylene glycol, heptamethylene glycol,octamethylene glycol, decamethylene glycol, glycerol, trimethylolpropaneand pentaerythritol; aromatic polyhydroxy compounds such ashydroquinone, resorcinol, catechol, m-xylylenediol, p-xylylenediol,4,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, bisphenol A,bisphenol S, bisphenol F, pyrogallol and phloroglycine; aliphaticpolyamines such as ethylenediamine, propylenediamine andhexamethylenediamine; aromatic polyamine compounds such asm-phenylenediamine, p-phenylenediamine, tolylenediamine,m-xylylenediamine and p-xylylenediamine; epoxy compounds such asbisphenol A diglycidyl ether, epoxy resins and diglycidyl terephthalate;and polymercaptan compounds such as ethanedithiol, 1,4-butanedithiol,trithioglycerin, dithiocatechol, dithioresorcinol, dithioquinol andtrithiophloroglycine.

The binder (C) used in this invention is not limited to the abovecompounds, and, for example, compounds having at least two kinds of theabove functional groups per molecule may also be used. Examples includeaminocarboxylic acids, hydroxycarboxylic acids, mercaptocarboxylicacids, aminobenzoic acids, hydroxybenzoic acids, mercaptobenzoic acids,aminoalcohols, and hydroxyanilines. The reaction products of the abovebinders with each other, for example a hydroxycarboxylic acid compoundobtained by reacting a polycarboxylic acid compound and polyol compound,may be equally used as the binder (C).

Among the above compounds, terephthalic acid, isophthalic acid, phthalicanhydride, trimellitic anhydride, pyromellitic anhydride,phenylenediamines, xylylenediamines, hexamethylenediamine, bisphenols,aminobenzoic acids, hydroxybenzoic acids and diepoxy compounds arepreferred because they are easily available and give desirableproperties.

The modified polyphenylene ether (A) and the modified polyolefin (B) canbe easily mixed in any desired ratios. But to achieve the object of thisinvention, the amount of the modified polyphenylene ether should be 5%to 95% by weight, preferably 20% to 80% by weight, based on the totalamount of the two. When the binder (C) is to be further mixed, itsamount is 0.01 to 10% by weight, preferably 0.01 to 5% by weight, basedon the total amount of the components (A), (B) and (C).

The amount of the modifier used in modifying the polyphenylene ether is0.001 to 20% by weight, preferably 0.01 to 10% by weight, morepreferably 0.01 to 5% by weight, based on the total amount of thepolyphenylene ether and the modifier. The total amount of the modifierand the vinyl or vinylidene compound used in modifying the polyolefin is0.01 to 50% by weight, preferably 0.01 to 30% by weight, more preferably0.1 to 20% by weight, based on the total amount of the polyolefin, themodifier and the vinyl or vinylidene compound. The ratio between themodifier and the vinyl or vinylidene compound is such that theproportion of the modifier is 1 to 90% by weight, preferably 10 to 50%by weight, based on the total weight of the two. Where a radicalinitiator is used in the modification of the polyphenylene ether and thepolyolefin, the amount of the radical initiator is 0.01 to 5 parts byweight, preferably 0.01 to 3 parts by weight, per 100 parts by weight ofthe polyphenylene ether or the polyolefin.

In order to permit the unique properties of the resin composition ofthis invention to be exhibited more effectively, organic amines such astrimethylamine, triethylamine, tri-n-butylamine and pyridine may beincorporated as adjuvants in the composition of this invention.

As required, the resin composition of this invention may further includeanother resin, an elastomer, and various additives such as fireretardants, fire-retardant aids, stabilizers, ultraviolet absorbers,plasticizers, lubricants, pigments, and fillers.

The following Referential Examples, Examples and Comparative Examplesillustrate the polyphenylene ether resin compositions provided by thisinvention.

REFERENTIAL EXAMPLE 1 Production of modified polyphenylene ether:

Maleic anhydride (90 g) and 15 g of dicumyl peroxide were added to 3 kgof a 2,6-dimethylphenol/2,3,6-trimethylphenol copolymer (containing 5mole % of 2,3,6-trimethylphenol) having an intrinsic viscosity of 0.47dl/g, measured in chloroform at 25° C., and they were mixed by aHenschel mixer. In a twin-screw extruder, the mixture was melt-kneadedat a temperature of 300° to 320° C. and pelletized.

Two grams of the pellets were dissolved in 50 ml of chloroform, and 500ml of methanol was added to the solution to precipitate the polymer. Thepolymer was separated by filtration and dried at 80° C. under reducedpressure for 10 hours. The resulting sample was analyzed byinfrared-absorption spectroscopy. The amount (% by weight) of maleicanhydride bonded to the polyphenylene ether was calculated by using acalibration curve obtained with polyphenylene ether and maleicanhydride. The amount of the bonded maleic anhydride so measured was1.1% by weight.

REFERENTIAL EXAMPLE 2 Production of modified polyphenylene ether:

Referential Example 1 was repeated except that dicumyl peroxide was notused. The amount of maleic anhydride bonded was 0.7% by weight.

REFERENTIAL EXAMPLE 3 Production of modified polyphenylene ether:

Referential Example 1 was repeated except that 90 g of glycidylmethacrylate was used instead of 90 g of maleic anhydride. A calibrationcurve of infrared-absorption spectroscopy was prepared from the resultsobtained with polyphenylene ether and glycidyl methacrylate. The amountof glycidyl methacrylate bonded was 1.3% by weight.

REFERENTIAL EXAMPLE 4 Production of modified polypropylene:

Three kilograms of polypropylene ("Idemitsu Polypro E-250G" produced byIdemitsu Petrochemical Co., Ltd.; melt index 1.0 g/10 min., density 0.90g/cm³) was mixed well with 90 g of maleic anhydride, 300 g of styreneand 15 g of dicumyl peroxide, and in a twin-screw extruder at 180° to220° C., the mixture was melt-kneaded and pelletized. Four grams of thepellets were extracted with methyl ethyl ketone for 24 hours using aSoxhlet extractor. The extraction residue was dried at 80° C. underreduced pressure for 10 hours, and then its weight was measured. Theextraction residue was subjected to infrared-absorption spectroscopy,and by using a calibration curve obtained with polypropylene,polystyrene and maleic anhydride, the amount (% by weight) of styreneand maleic anhydride bonded to polypropylene were calculated. The totalamount of bonded maleic anhydride and styrene so determined was 6.5% byweight.

REFERENTIAL EXAMPLE 5 Production of modified polypropylene:

Referential Example 4 was repeated except that 90 g of glycidylmethacrylate was used instead of 90 g of maleic anhydride. A calibrationcurve of infrared-absorption spectroscopy was obtained withpolypropylene, polystyrene and glycidyl methacrylate. The total amountof styrene and glycidyl methacrylate bonded was 6.2% by weight.

EXAMPLE 1

A mixture of 25 g of the maleic anhydride-modified polyphenylene etherpellets obtained in Referential Example 1 and 25 g of the modifiedpolypropylene pellets obtained in Referential Example 5 was melt-kneadedat 270° C. and 60 rpm for 10 minutes using a laboplastomill. A 0.3 mmthick sheet was prepared by press-forming the resulting resincomposition at 270° C. under a pressure of 200 kg/cm². A test piecedescribed in ASTM D412 C was punched out and its tensile strength andelongation were measured.

The resin composition was extracted with chloroform as a solvent using aSoxhlet extractor. The extraction residue was dried at 80° C. underreduced pressure for 10 hours, and then its weight was measured. Theproportion of a chloroform-insoluble portion was calculated on the basisof the difference of the measured weight from the weight of the resincomposition before extraction, and made a measure of evaluation of itssolvent resistance. By a Koka-type flow tester, the melt flow value(cc/sec) of the resin composition at 230° C. under a load of 60 kg wasmeasured.

The results are shown in Table 1. A comparison of these results withthose of Comparative Examples 1 to 4 given hereinbelow shows that theresin composition of this invention has an excellent balance amongsolvent resistance, mechanical strength and moldability not seen inconventional polyphenylene ether/polyolefin compositions, and judgingfrom its elongation, it also has excellent compatibility. Incidentally,a composition composed of unmodified polyphenylene ether and polystyrenein a weight ratio of 50:50 has a melt flow value of 2.0×10⁻³ cc/sec.

EXAMPLE 2

A mixture composed of 49.5% by weight of the

modified polyphenylene ether obtained in Referential Example 2, 49.5% byweight of modified polypropylene obtained in Referential Example 5, and1% by weight of p-phenylenediamine was melt-kneaded in the same way asin Example 1, and molded to prepare test specimens. The properties ofthe test specimens were measured, and the results are shown in Table 1.

A 0.1 mm thick sample cut out from the composition obtained bymelt-kneading was observed under an electron microscope. It wasdetermined that the modified polyphenylene ether was dispersed inparticles having a size of about 0.5 to 1.5 micrometers. In contrast, inthe sample obtained in Comparative Example 4, the dispersedpolyphenylene ether had a size of about 5 to 10 micrometers.

COMPARATIVE EXAMPLE 1

Example 1 was repeated except that the unmodified polyphenylene etherused in Referential Example 1 and the unmodified polypropylene used inReferential Example 4 were used instead of the modified polyphenyleneether and the modified polyolefin respectively. The results are shown inTable 1.

REFERENTIAL EXAMPLE 6

Production of modified polypropylene using only a vinyl compound:

Referential Example 5 was repeated except that glycidyl methacrylate wasnot used. The amount of styrene bonded was 5.5% by weight.

REFERENTIAL EXAMPLE 7

Production of modified polypropylene using only the modifier:

Referential Example 5 was repeated except that styrene was not used. Theamount of the modifier bonded was 0.7% by weight.

COMPARATIVE EXAMPLE 2

Comparative Example 1 was repeated except that the modifiedpolypropylene obtained in Referential Example 6 was used instead of theunmodified polypropylene. The results are shown in Table 1.

COMPARATIVE EXAMPLE 3

Comparative Example 1 was repeated except that the modifiedpolypropylene obtained in Referential Example 7 was used instead of theunmodified polypropylene. The results are shown in Table 1.

COMPARATIVE EXAMPLE 4

Comparative Example 1 was repeated except that the modifiedpolypropylene obtained in Referential Example 5 was used instead of theunmodified polypropylene. The results are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Ex. (Ex-                                                                      ample) or                   Chloroform-                                       CEx. (Com-                                                                             Tensile  Elonga-   insoluble                                                                              Melt flow                                parative strength tion      portion  value                                    Example) (kg/cm.sup.2)                                                                          (%)       (wt. %)  (cc/sec.)                                ______________________________________                                        Ex. 1    360      7.2       70       0.45                                     Ex. 2    430      20.6      82       0.1                                      CEx. 1   180      3.1       49       --                                       CEx. 2   250      3.3       48       0.20                                     CEx. 3   100      2.0       48       0.58                                     CEx. 4   270      5.1       47       0.25                                     ______________________________________                                    

EXAMPLES 3 AND 5

Example 1 was repeated except that the modified polyphenylene ether andthe modified polypropylene were used in the proportions shown in Table2. The results are shown in Table 2.

EXAMPLES 4 AND 6

Example 2 was repeated except that the modified polyphenylene ether,modified polypropylene and p-phenylenediamine were used in theproportions shown in Table 2.

COMPARATIVE EXAMPLES 5-6

Comparative Example 4 was repeated except that the polyphenylene etherand modified polypropylene were used in the proportions shown in Table2. The results are also shown in Table 2.

                  TABLE 2                                                         ______________________________________                                                                        Chloro-                                                                              Melt                                                           Elon-   form-  flow                                                  Tensile  ga-     insoluble                                                                            value                                  Composition    strength tion    portion                                                                              (cc/                                   (% by weight)  (kg/cm.sup.2)                                                                          (%)     (wt. %)                                                                              sec)                                   ______________________________________                                        Ex. 3 MAH-modified 385      6.8   50     0.22                                       PPE/GM.St-                                                                    modified PP                                                                   (70/30)                                                                 Ex. 4 MAH-modified 450      13.3  51     0.07                                       PPE/Gm.St-                                                                    modified PP/                                                                  p-phenylene-                                                                  diamine                                                                       (69.5/29.5/1)                                                           CEx. 5                                                                              PPE/GM.St-   300      3.8   28     0.16                                       modified PP                                                                   (70/30)                                                                 Ex. 5 MAH-modified 329      8.7   85     0.54                                       PPE/GM.St-                                                                    modified PP                                                                   (30/70)                                                                 Ex. 6 MAH-modified 405      21.4  87     0.23                                       PPE/GM.St-                                                                    modified PP/                                                                  p-phenylene-                                                                  diamine                                                                       (29.5/69.5/1)                                                           CEx. 6                                                                              PPE/GM.St-   297      5.8   68     0.46                                       modified PP                                                                   (30/70)                                                                 ______________________________________                                         Note                                                                          MAH: maleic anhydride; GM: glycidyl methacrylate; St: styrene; PPE:           polyphenylene ether; PP: polypropylene.                                  

EXAMPLE 7

Example 2 was repeated except that 49% by weight of the modifiedpolyphenylene ether, 49% by weight of the modified polypropylene, and 2%by weight of p-aminobenzoic acid instead of p-phenylenediamine as abinder were used, and 0.5 part by weight, per 100 parts by weight of themixture of the above compounds, of tri-n-butylamine was added as areaction aid. The results are shown in Table 3.

EXAMPLE 8

Example 7 was repeated except that bisphenol A was used as the binder.The results are shown in Table 3.

The effect of the binders was seen in Examples 2, 7 and 8.

EXAMPLE 9

Example 1 was repeated except that the modified polyphenylene etherobtained in Referential Example 3 and the modified polypropyleneobtained in Referential Example 4 were used as the resin components. Theresults are shown in Table 3.

EXAMPLES 10 AND 11

Example 9 was repeated except that the proportion of each of themodified polyphenylene ether and the modified polypropylene wasdecreased to 49% by weight, and as a binder, 2% by weight ofp-phenylenediamine (Example 10) or bisphenol A (Example 11) was added.The results are shown in Table 3.

EXAMPLE 12

Example 8 was repeated except that 48% by weight of the modifiedpolyphenylene ether obtained in Referential Example 2, 48% by weight ofthe modified polypropylene obtained in Referential Example 4 and 4% byweight of bisphenol A as a binder were mixed, and 0.5 part by weight,per 100 parts by weight of the mixture, of tri-n-butylamine as areaction aid was added. The results are shown in Table 3.

EXAMPLE 13

Example 10 was repeated except that the modified polyphenylene etherobtained in Referential Example 3 and the modified polypropyleneobtained in Referential Example 5 were used. The results are shown inTable 3.

EXAMPLE 14

Example 12 was repeated except that the modified polyphenylene etherobtained in Referential Example 3, the modified polypropylene obtainedin Referential Example 5 and terephthalic acid as a binder were used.The results are shown in Table 3.

EXAMPLE 15

Example 12 was repeated except that an epoxy resin ("Epikote 1009", aproduct of Yuka-Shell Co., Ltd.) was used instead of bisphenol A as abinder. The results are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                                                       Chloroform-                                             Tensile     Tensile   insoluble                                               strength    elongation                                                                              portion                                        Example  (kg/cm.sup.2)                                                                             (%)       (wt. %)                                        ______________________________________                                         7       308         14.7      73                                              8       324         15.5      67                                              9       310          7.3      66                                             10       363         10.4      76                                             11       349         12.9      74                                             12       290          9.8      69                                             13       310         11.0      70                                             14       325         12.4      75                                             15       337         14.6      79                                             ______________________________________                                    

Referential Example 8

Production of modified polypropylene:

Three kilograms of polypropylene ("Idemitsu Polypro E-250G" produced byIdemitsu Petrochemical Co., Ltd.; melt index 1.0 g/10 min., density 0.90g/cm³) was mixed well with 90 g of 2-hydroxyethyl acrylate, 300 g ofstyrene and 15 g of dicumyl peroxide, and in a twin-screw extruder at180° to 220° C., the mixture was melt-kneaded and pelletized. Four gramsof the pellets were extracted with chloroform for 24 hours using aSoxhlet extractor. The extraction residue was dried at 80° C. underreduced pressure for 10 hours, and then its weight was measured. Theextraction residue was subjected to infrared-absorption spectroscopy,and by using a calibration curve obtained with polypropylene,polystyrene and 2-hydroxyethyl acrylate, the amount (% by weight) ofstyrene and 2-hydroxyethyl acrylate bonded to polypropylene werecalculated. The amount of bonded styrene was 6.5% by weight, and theamount of bonded 2-hydroxyethyl acrylate was 1.9% by weight.

REFERENTIAL EXAMPLE 9

Production of modified polypropylene:

Referential Example 8 was repeated except that the amount of2-hydroxyethyl acrylate was changed to 120 g. The amount of bondedstyrene was 6.2% by weight, and the amount of 2-hydroxyethyl acrylatebonded was 3.5% by weight.

REFERENTIAL EXAMPLE 10

Production of modified polypropylene:

Referential Example 8 was repeated except that 2-hydroxypropylmethacrylate was used instead of 2-hydroxyethyl acrylate. The amount ofbonded styrene was 6.2% by weight, and the amount of bonded2-hydroxypropyl methacrylate was 2% by weight.

REFERENTIAL EXAMPLE 11

Referential Example 8 was repeated except that 160 g ofbis-2-hydroxyethyl maleate was used instead of 90 g of 2-hydroxyethylacrylate. The amount of bonded styrene was 6.1% by weight, and theamount of bonded bis-2-hydroxyethyl maleate was 2.5% by weight.

EXAMPLE 16

A mixture of 25 g of the maleic anhydride-modified polyphenylene etherpellets obtained in Referential Example 2 and 25 g of the modifiedpolypropylene pellets obtained in Referential Example 8 was melt-kneadedat 270° C. and 60 rpm for 10 minutes using a laboplastomill. A 0.3 mmthick sheet was prepared by press-forming the resulting resincomposition at 270° C. under a pressure of 200 kg/cm². A test piecedescribed in ASTM D412 C was punched out and its tensile strength andelongation were measured.

The resin composition was extracted with chloroform as a solvent using aSoxhlet extractor. The extraction residue was dried at 80° C. underreduced pressure for 10 hours, and then its weight was measured. Theproportion of a chloroform-insoluble portion was calculated on the basisof the difference of the measured weight from the weight of the resincomposition before extraction, and made a measure of evaluation of itssolvent resistance. By a Koka-type flow tester, the melt flow value(cc/sec) of the resin composition at 230° C. under a load of 60 kg wasmeasured.

The results are shown in Table 4. A comparison of these results withthose of Comparative Examples 1, 2, 7 and 8 given in Table 4 shows thatthe resin composition of this invention has an excellent balance amongsolvent resistance, mechanical strength and moldability not seen inconventional polyphenylene ether/polyolefin compositions, and judgingfrom its elongation, it also has excellent compatibility. Incidentally,a composition composed of unmodified polyphenylene ether and polystyrenein a weight ratio of 50:50 has a melt flow value of 2.0×10⁻³ cc/sec.

EXAMPLE 17

A mixture composed of 49.75% by weight of the modified polyphenyleneether obtained in Referential Example 1, 49.75% by weight of modifiedpolypropylene obtained in Referential Example 9, and 0.5% by weight oftri-n-butyl amine was melt-kneaded in the same way as in Example 16, andmolded to prepare test specimens. The properties of the test specimenswere measured, and the results are shown in Table 4.

A 0.1 mm thick sample cut out from the composition obtained bymelt-kneading was observed under an electron microscope. It wasdetermined that the modified polyphenylene ether was dispersed inparticles having a size of about 1.0 to 2.0 micrometers. In contrast, inthe sample obtained in Comparative Example 8, the dispersedpolyphenylene ether had a size of about 5 to 10 micrometers.

REFERENTIAL EXAMPLE 12

Production of modified polypropylene using only the modifier:

Referential Example 9 was repeated except that styrene was not used. Theamount of 2-hydroxyethyl acrylate bonded was 3.5% by weight.

Comparative Example 1 was repeated except that the modifiedpolypropylene obtained in Referential Example 12 was used instead of thepolypropylene. The results are shown in Table 4.

COMPARATIVE EXAMPLE 8

Comparative Example 1 was repeated except that the modifiedpolypropylene obtained in Referential Example 9 was used instead of thepolypropylene. The results are shown in Table 4.

EXAMPLE 18

Example 17 was repeated except that the modified polyphenylene etherobtained in Referential Example 1 and the modified polypropyleneobtained in Referential Example 10 were used as the resin components.The results are shown in Table 4.

EXAMPLE 19

Example 17 was repeated except that the modified polyphenylene etherobtained in Referential Example 1 and the modified polypropyleneobtained in Referential Example 11 were used as the resin components.The results are shown in Table 4.

                  TABLE 4                                                         ______________________________________                                        Tensile       Elon-   Chloroform- Melt flow                                   strength      gation  insoluble   value                                       (kg/cm.sup.2) (%)     portion (%) (cc/sec)                                    ______________________________________                                        Ex. 16  360       7.2     60        0.45                                      Ex. 17  380       10.3    67        0.41                                      CEx. 1  180       3.1     49        --                                        CEx. 2  250       3.3     48        0.2                                       CEx. 7  127       2.2     48        0.58                                      CEx. 8  270       5.1     47        0.25                                      CEx. 18 360       7.4     61        --                                        CEx. 19 354       8.3     64        --                                        ______________________________________                                    

As can be seen from the results of Examples and Comparative Examples,the resin compositions of this invention provide molding materialshaving better solvent resistance, moldability and mechanical strengththan known resin compositions of polyphenylene ethers and polyolefinsand an excellent balance among these properties. These molding materialsare useful in such applications as automobiles and electrical andelectronic component parts.

What is claimed is:
 1. A solvent-resistant polyphenylene ether resincomposition comprising(A) a modified polyphenylene ether obtained bymodifying a polyphenylene ether with a modifier selected from the groupconsisting of maleic anhydride, glycidyl methacrylate and glycidylacrylate in the absence of a radical initiator, and (B) a modifiedpolyolefin obtained by modifying a polyolefin with styrene and amodifier selected from the group consisting of maleic anhydride,glycidyl methacrylate and glycidyl acrylate in the presence of a radicalinitiator.
 2. The composition of claim 1 wherein the modifier for thepolyphenylene ether is maleic anhydride and the modifier for thepolyolefin is glycidyl methacrylate or glycidyl acrylate.
 3. Thecomposition of claim 1, wherein the polyphenylene ether ispoly(2,6-dimethyl-1,4-phenylene)ether or2,6-dimethylphenol/2,3,6-trimethylphenol copolymer.
 4. The compositionof claim 1 wherein the polyolefin is polypropylene.